Substituted carbonyl-carbamidyl-benzimidazole-2-yl-carbamic acid esters

ABSTRACT

1-(N-(ALKYL, CYCLOALKYL, PHENYL OR SUBSTITUTED PHENYL)-SOR -O-CARBONYL-CARBAMIDYL)-BENZIMIDAZOLE-2-YL-CARBAMIC ACID ALKYL ESTERS, WHICH POSSESS FUNGICIDAL PROPERTIES AND WHICH MAY BE PRODUCED BY CONVENTIONAL METHODS.

United States Patent 3,711,503 SUBSTITUTED CARBONYL-CARBAMIDYL-BENZ-IMIDAZOLE-Z-YL-CARBAMIC ACID ESTERS Arno Widdig, Blecher, Klaus Sasse,Schildgen, Ferdinand Grewe, Burscheid, and Hans Sclreinpflug, Paul-ErnstFrohberger, and Helmut Kaspers, Leverkusen, Germany, assignors t0Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany N0 Drawing.Filed June 30, 1970, Ser. No. 51,381 Claims priority, applicationGermany, July 16, 1969, P 19 36 130.9 Int. Cl. C07d 49/38 US. Cl.260-309.2 9 Claims ABSTRACT OF THE DISCLOSURE 1- [N-(alkyl, cycloalkyl,phenyl or substituted phenyl)-S- orO-carbonyl-carbamidyl]benzimidazole-Z-yl-carbamic acid alkyl esters,which possess fungicidal properties and which may be produced byconventional methods.

The present invention relates to and has for its objects the provisionof particular new l-[N-(alkyl, cycloalkyl, phenyl or substitutedphenyl)-S- or O-carbonyl-carbamidyl]benzimidazole-Z-yl-carbamic acidalkyl esters, which possess fungicidal properties, active compositionsin the form of mixtures of such compounds with solid and liquiddispersible carrier vehicles, and methods for producing such compoundsand for using such compounds in a new Way especially for combatingfungi, with other and further objects becoming apparent from a study ofthe within specification and accompanying examples.

It is known that N-trichloromethylthiotetrahydrophthalimide can be usedas a fungicide (A) (cf. US. patent specification 2,553,770). It hasmoreover attained considerable importance in practice. Although thisfungicide does have a broad spectrum of activity, there are neverthelessmany phytopathogenic fungi against Which it is inelfective orinadequately effective. Moreover, it has no systemic activity worthmentioning.

It has now been found, in accordance with the present invention, thatparticular new benzimidazole derivatives of the general formula in whichX stands for oxygen or sulfur,

R stands for lower alkyl, and

R stands for alkyl with to 12 carbon atoms (when X stands for oxygen),or for alkyl with 1 to 12 carbon atoms (when X stands for sulfur), orfor cycloalkyl with 5 to 12 carbon atoms, or for (possibly substituted)aryl or aralkyl.

Preferably,

R stands for alkyl with 1 to 3 carbon atoms,

R stands for alkyl such as n-butyl, n-octyl or n-dodecyl or for(possibly substituted) phenyl or cyclohexyl,

exhibit strong fungicidal properties.

ICC

It has been furthermore found, in accordance with the present inventionthat a process for the production of a benzimidazole of the Formula Iabove in which a benzimidazole-Z-carbamic acid ester of the formula inwhich R is the same as defined above is reacted with an isocyanate ofthe formula 0ONC--XR (III) in which X and R are the same as definedabove in the presence of a diluent.

Surprisingly, the benzimidazoles according to the present invention showa higher fungicidal activity than the above-mentionedN-trichloromethylthiotetrahydrophthalimide. The compounds according tothe present invention therefore represent a valuable contribution to theart.

When benzimidazole-Z-carbamic acid methyl ester and4-tert.-butylphenoxycarbonylisocyanate are used as starting materials,the reaction course can be represented by the following formula scheme:

(IIIa) The benzimidazole-Z-carbamic acid esters used as startingmaterials are clearly defined by the Formula II above.

As examples of benzimidazole-Z-carbamic acid esters, there may bementioned: benzimidazole-Z-carbamic acid methyl ester,benzimidazole-Z-carbamic acid ethyl ester, and the like.

The benzimidazolecarbamic acid esters to be used as starting materialsare known; they may be prepared for example from o-phenylenediamines andN-cyanocarbamic acid esters in acetic acid solution (cf. South Africanpatent application 67/6509).

The isocyanates required as starting materials are prepared for examplefrom chlorocarbonylisocyanate and alcohols or phenols, orchlorocarbonylisocyanate and alcohols or phenols or mercaptans in inertsolvents, such as in diethyl ether (of. in this connection German patentapplication P 17 93 088.0). They are generally defined by the FormulaIII above.

As examples of isocyanates, there may be mentioned: octoxycarbonylisocyanate, butylmercaptocarbonyl isocyanate, dodecylmercaptocarbonylisocyanate, cyclohexoxycarbonyl isocyanate, phenylmercapto-carbonylisocyanate, 4-tert.-butylphenoxycarbonyl isocyanate and phenoxycarbonylisocyanate.

The diluent used in the process according to the present invention maybe any organic solvent inert to isocyanates. Preferred examples includehydrocarbons, such as benzine and benzene; chlorinated hydrocarbons,such as chlorobenzene and chloroform; ethers, such as diethyl ether anddioxan; and mixtures of these solvents.

The reaction temperatures can be varied within a fairly wide range. Ingeneral, the reaction is carried out at from substantially between aboutto 80 C., preferably between about to 50 C.

When carrying out the production process according to the invention, thereactants are preferably used in substantially equimolar amounts.Amounts smaller or greater by up to 20% are possible without substantialloss of yield.

The present active compounds have not only the good properties ofoutstanding commercial agents but also other great advantages. One istheir ability to penetrate into the plant and be conducted systemicallyand so act fungitoxically away. from the place of application. They canbe taken up by the seed surface or the roots or abovethe-soil organs ofplants after etxernal application. Another advantage is the ability tobecome loco-systemically active, i.e. to exercise deep action in planttissue and eliminate fungal pathogens which have already penetrated intothe plant tissue. Moreover, the present substances are much moreeffective than known commercial agents against various fungal plantdisease organisms, such as apple scab, Piricularia and Pellicularia,bunt of wheat and many phytopathogenic soil fungi. They are alsoelfective against mold fungi, yeasts and bacteria, indeed even againstinsects and mites.

As crop protection agents, the present substances can be used forexample for soil treatment, seed treatment and treatment ofabove-the-soil parts of plants. They are particularly effective againstFusicladium dend'riticum, Erysiphe cichoracearwm, Podosphaeraleucotricha, Piricwlaria oryzae, Pellicularia sasakii, Tilletia caries,Erysz'phe graminis, Sclerotinia sclerotiorum, Verticillium alboatrum,Thz'elaviopsis basicola, Fusarium culmorwm, F usarium oxysporum,Fusariwm dianthi, Phialophora cinerescens and Cercospora musae.

The present substances are well tolerated by plants. The followingattributes facilitate their handling by humans: they have only a slighttoxicity to warm-blooded animals; they have only a slight odor; there isno deleterious effect on human skin.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e. plant compatible or herbicidally inert)pesticide'diluents or extenders, i.e. diluents or extenders of the typeusable in conventional pesticide formulations or compositions, e.g.conventional pesticide dispersible carrier vehicles, such as solutions,emulsions, suspensions, emulsifiable concentrates, spray powders, oils,pastes, soluble powders, dusting agents, granules, tablets, etc. Theseare prepared in known manner, for instance by extending the activecompounds with conventional pesticide dispersible liquid diluentcarriers and/ or dispersible solid carriers optionally with the use ofcarrier vehicle assistants, e.g. conventional pesticide surface-activeagents, including emulsifying agents and/or dispersing agents, whereby,for example, in the case where water is used as diluent, organicsolvents may be added as auxiliary solvents. The following may bechiefly considered for use as conventional carrier vehicles for thispurpose: inert dispersible liquid diluent carriers including inertorganic solvents and non-solvents, such as aromatic hydrocarbons (e.g.benzene, toluene, xylene, dimethyl naphthalene, aromatic naphthas,etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g.chlorobenzenes, etc.), paraflins (e.g. petroleum fractions), chlorinatedaliphatic hydrocarbons (e.g. methyl chloride, etc.), alcohols (e.g.methanol, ethanol, propanol, butanol, etc.), amines ,(e.g. ethanolamine,etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.),amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethylsulfoxide, etc.), ketones (e.g. acetone, etc.), and/or water; as well asinert dispersible finely divided solid carriers, such as ground naturalminerals (e.g. kaolins, alumina, silica, chalk, i.e. calcium carbonate,talc, kieselguhr, diatomaceous earth, clay montmorillonite, etc.), andground synthetic minerals (e.g. highly dispersed silicic acid,silicates, e.g. alkali silicates, etc.); Whereas the following may bechiefly considered for use as conventional carrier vehicle assistants,e.g. surface-active agents, for this purpose: emulsifying or wettingagents, such as non-ionic and/or anionic emulsifying or wetting agents.(e.g. polyethylene oxide esters of fatty acids, polyethylene oxideethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., andespecially alkyl aryl-polyglycol ethers, magnesium stearate, sodiumoleate, etc.); and/ or dispersing agents such as lignin, sulfite wasteliquors, methyl cellulose, etc.

Such active compounds may be employed alone or in.

the form of mixtures with one another and/ or with such solid and/orliquid dispersible carrier vehicles and/or with other known compatibleactive agents, especially plant protection agents, such as otherfungicides, or herbicides, insecticides, acaricides, nematocides,bactericides, etc., including, especially fungicidal, organo-phosphoruscompounds, carbamate compounds, dithiocarbamate compounds, chlorinecompounds, dinitro compounds, organic sulfur or copper compounds,substituted phenoxy compounds, chlorophenols, substituted diphenylethers,

anilide compounds, ureas, triazines, antibiotics, and other knownagricultural chemicals and/ or fertilizers, if desired, or in the formof particular dosage preparations for specific application madetherefrom, such as solutions, emulsions, suspensions, powders, pastes,and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 0.l-95%, and preferably0.5- by weight of the mixture, whereas carrier composition mixturessuitable for direct application or field application generallycontemplate those in which the active compound is present in an amountsubstantially between about 0.001-10%, preferably 0.01-5%, by weight ofthe mixture. Thus, the present invention contemplates over-allcompositions which comprise mixtures of a conventional dispersiblecarrier vehicle such as (1) a dispersible inert finely divided carriersolid, and/or (2) a dispersible liquid such as an inert organic solventand/ or water preferably including a surface-active effective amount ofa carrier vehicle assistant, e.g. a surface-active agent, such 'as anemulsifying agent and/or a dispersing agent, and an amount of the activecompound which is effective for the purpose in question and which isgenerally about 0.00l-%, and preferably 0. 0l95%, by weight of themixture.

Generally, the active compound is used in dosage amounts per unit areaof substantially between about 154,000 g., preferably 40-600 g., andmost preferably 40-100 g., per 10 areas, irrespective of the presence orabsence of such carrier vehicle.

The active compounds can also be used in accordance with the well-knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. average particle diameter of from 50-100 microns; oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 1 quart/acre, preferably 2-l6 fluidounces/acre, are sufiicient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95% by weight of the activecompound, or even the active substance alone, e.g. about 20100% byweight of the active compound.

In particular, the present invention contemplates methods of selectivelykilling, combating or controlling fungi, which comprise applying to atleast one of (a) such fungi and (b) their habitat, i.e. the locus to beprotected, a fungicidally eifective or toxic amount of the particularactive compound of the invention alone or together with a carriervehicle as noted above. The instant formulations or compositions areapplied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, sprinkling, pouring, drydressing, moist dressing, wet dressing, paste dressing, viaincrustation; and the like.

Significantly, the fungicidal compositions of the present invention canbe applied for example by spraying a dust formualtion directly ontostems and leaves of plants; or by using the formulation as aseed-dressing; by spraying an emulsifiable concentrate, diluted withwater, etc. to a desirable concentration, onto stems and leaves ofplants; by suspending a wettablc powder in water at a desirableconcentration, onto stems and leaves of plants; by suspending a wettablepowder in water at a desirable concentration and spraying theformulation onto stems and leaves of plants; by applying granuleformulations to the soil, and the like.

When the compounds are used as leaf fungicides, the concentrations ofactive compound in the application forms can be varied within a fairlywide range. They are, in general, from 0.5 to 0.0005, preferably 0.2 to0.001, percent by weight.

In the case of seed treatment, there are required, in general, amountsof active compound of 001-50 g., preferably 0.5- g., per kilogram ofseed.

For soil treatment, amounts of active compound of 1-1000 g., preferablyfrom -200 g., per cubic meter of soil are generally necessary.

'It will be realized, of course, that the concentration of theparticular active compound utilized in admixture with the carriervehicle will depend upon the intended application, the purpose for whichthe active compound is used, and the like. Therefore, in special cases,it is possible to go above or below the aforementioned concentrationranges and dosage amounts per unit area.

The fungicidal effectiveness of the particular new compounds of thepresent invention is illustrated, Without limitation, by the followingexamples:

EXAMPLE 1 Erysiphe test Solvent: 4.7 parts by weight acetone Emulsifier:0.3 part by weight alkylaryl polyglycol ether Water: 95.0 parts byweight The amount of the particular active compounds required for thedesired final concentration in the spray liquid is mixed with the statedamount of solvent, and the resulting concentrate is then diluted withthe stated amount of water containing the stated emulsifier.

Young cucumber plants (Delikatess variety) with about three foliageleaves are sprayed with the given spray liquid until dripping wet. Thecucumber plants remain in a green-house for 24 hours to dry. Such plantsare then, for the purpose of inoculation, dusted with conidia of thefungus Erysiphe polyphaga. The plants are subsequently placed in agreen-house at 23-24 C. and at a relative atmospheric humidity of about75%.

After 12 days, the infestation of the cucumber plants is determined as apercentage of the untreated but also inoculated control plants. 0% meansno infestation; 100% that the infestation is exactly as great as in thecase of the control plants.

The particular active compounds tested, their concentrations, and theresults obtained can be seen from the following Table 1.

TABLE 1.ERYSIPHE TEST Infection as a percentage of the infection of theuntreated control with a concentration of active compound of Activecompound 0.025

/ -SC C13 0 0 (known) l (H) N NH- C-O OH:

L (H) N NH- C-0 0 H3 l O/ NH-fiO-CaH 7-n J (i N NH--G--O OH:

| O NHCSC|Hnn N L g N NH-C-O OH:

I O O NH|J S-OizHz5- t N NH-G-O OH:

EXAMPLE 2 Erysiphe test (systemic) Solvent: 4.7 parts by weight acetoneEmulsifier: 0.3 part by weight alkylaryl polyglycol ether Water: 95.0parts by weight The amount of the particular active compound requiredfor the desired final concentration in the treatment liquid is mixedwith the stated amount of the solvent, and the resulting concentrate isthen diluted with the stated amount of water containing the statedemulsifier.

Cucumber plants grown in standard soil are, in the 1-2 leaf stage,watered, within one week, thrice/once with 20 cc. of the liquid to beused for watering, in the stated concentrations of active compound, withreference to 100 cc. of soil.

The plants thus treated are, after treatment, inoculated with conidia ofthe fungus Erysiphe cichoracearum. The plants are subsequently placed ina green-house at 2324 C. and at a relative atmospheric humidity of about70%.

After 12 days, the infection of the cucumber plants is determined as apercentage of the untreated but also inoculated control plants.

0% means no infection; whereas 100% means that the infection is exactlyas great .as in the case of the control plants.

The particular active compounds tested, their concentrations and the.results obtained can be seen from the following Table 2.

TABLE 2.-ERYSIPHE TEST (SYSTEMIC) guhr to give a finely powdered mixturewith the desired concentration of the particular active compound.

For seed treatment, the barley seed is shaken with the extended activecompound in a closed glass flask. Three batches of 12 grains of seed aresown 2 cm. deep in a mixture of one part by volume of Fruhstorferstandard soil and one part by volume of quartz sand in flowerpots.Germination and emergence takes place under favorable conditions in agreenhouse 7 days after sowing, when the barley plants have unfoldedtheir first leaf, they are dusted with fresh spores of Erysiphe graminisvar. hordei and further cultivated at 21-22 C. and 70% relativeatmospheric humidity and 16 hours exposure to light.

Infection as a percentage of the untreated control with a concentrationof active compound of Active compound 120 ppm.

NS-C Cl; 100

(known) NlNH-C 0-0 OH:

I 0 O NH'GO O CBHI7 H NiNH-C 0-0 CH3 I 0 NH-C O-SC4H n I NH-C 0-0 CH:\N/ n I O J (H) N NHC-O CH:

EXAMPLE 3 Powdery mildew of barley (systemic) Application of theparticular active compounds takes place as powder-form seed treatmentagent. They are produced by extending the given active compoundconcerned with a mixture of equal parts by weight of talc and kiesel- 75infection.

The particular active compounds tested, the concentrations of activecompound in the seed treatment agent as well as the amount appliedthereof and the percentage mildew infection can be seeen from thefollowing Table 3.

leaf stage, watered once within one week with cc. of the liquid to beused for Watering, in the stated concentration of active compound, withreference to 100 cc. of soil.

TABLE 3.-POWDERY MILDEW 0F BARLEY (SYSTEMIC) Concentration of activecom- Infection as pound in the Amount :1 percentage dressing, applied ofof the percent by dressing in untreated Active compounds weight g./kg.seed control N ondressed- 100 N-- S-C Ola (known) NLNHC 0-0 OH:

I O=C-NH-C 0-S- F NJNHCO-O OH:

I 0=CNHC OO'CEH17II EXAMPLE 4 Fusicladium test (systemic) Solvent: 4.7parts by weight acetone Emulsifier: 0.3 part by weight alkylarylpolyglycol ether Water: 95.0 parts by weight Active compound The plantsthus treated are, after treatment, inoculated with an aqueous conidiumsuspension of Fusicladium dendriticum and incubated for 18 hours in ahumidity chamber kept at 18-20 C. and at an atmospheric humidity of Theplants are then again placed in a greenhouse for 14 days.

15 days after inoculation, the infection of the seedlings is determinedas a percentage of the untreated but also inoculated control plants. 0%means no infection; whereas 100% means that the infection is exactly asgreat as in the case of the control plants.

The particular active compounds tested, their concentrations and theresults obtained can be seen from the following Table 4.

TABLE 4.-FUSICLADIUM TEST (SYSTEMIC) Infection as a percentage of theinfection of the untreated control with a concentration of activecompound of p.p.m.

N-s-oon (known) TABLE 4Continued Active compound NJ-NHF-C 0-0 CHI NLNHFCO O CHI Infection as a percentage of the infection of the untreatedcontrol with a concentration of active compound of 120 p.p.m.

EXAMPLE 5 Fusicladium test (apple scab) [Curative] Solvent: 4.7 parts byweight acetone Emulsifier: 0.3 part by weight alkylaryl polyglycol etherWater: 95.0 parts by weight at 18-20 C. and at an atmospheric humidityof The plants are then again placed in a greenhouse where they dry.

After standing for a suitable period of time, the plants are thensprayed until dripping wet with the given spray liquid prepared in themanner described above. The plants are then again placed in agreenhouse.

15 days after inoculation, the infestation of the apple seedlings isdetermined as a percentage of the untreated but also inoculated controlplants.

0% means no infestation; whereas 100% means that.

the infestation is exactly as great as in the case of the controlplants.

The particular active compounds tested, their concentrations, the periodof time between inoculation and spraying and the results obtained can beseen from the following Table 5.

TABLE 5.-FUSICLADIUM TEST (CURATIVE) [Residence period in hours: 42]

Infection as a percentage of the infection of the untreated control witha concentration of active compound Active compound 0. 1 0. 025

(A) C O 100 100 SC 01s (known) I Nl-NHC 0-0 CHa l 0 NH (Ht-Q 3 0 24 FNLNHC O-O CH3 1 /C\ o NH-C O-O-CSHlr-Il NiNHC O-O CH3 0 NH-O0SC4Ho-n NJNBFC O 0 CH:

O NH-(fll- S-CnHw-n J (H) N NH-C-O CH;

J (H) N NHC--O CH3 o NH-("3O( s)s EXAMPLE-6 vent, and the concentrate isdiluted with the stated amount Dispersing agent: 0.05 part by weightsodium oleate Water: 95.75 parts by weight H O Other additives: 0.20part by weight gelatin The amount of the particular active compoundrequired for the desired concentration of such active compound in ofwater containing the stated additives.

Two batches each consisting of rice plants about 2-4 Weeks old aresprayed with the spray liquor until dripping wet. The plants remain in agreen-house at temperatures of 22 to 24 C. and a relative atmospherichumidity of about 70% until they are dry. One batch of the plants isthen inoculated with an aqueous suspension of 100,000 to 200,000spores/ml. of Piricularia the spray liquor is mixed with the statedamount of soloryzae and placed in a chamber at 2426 C. and

15 relative atmospheric humidity. The other batch of the plants isinfected with a culture of Pellicularia sasakii grown on malt agar andplaced in a chamber at 28-30 16 active compound, however, being appliednot before, but only 16 hours after, inoculation.

The particular active compounds tested, their concen- C. and 100%relative atmospheric humidity. trations and the results obtained canalso be seen from 5 to 8 days after inoculation, the infection of allthe 5 the following Table 6.

i TABLE 6.PIRICULARIA AND PELLICULARIA TEST pr.=protective cur.=curativeInfection as a percentage of the infection of the untreated control witha. concentration of active compound of Active compound 0.05 0.025 0.05 20.025

(A)..... pr. 25 100 cur. 100

N S0 Gla (known) 3 .;I::. V r.- 0 0 0 0 -TI ur. 25

NiNH-C O-O CH 1 /C\ o un-o OO-C8HlT-n 4 --;:r.' I. O 0 0 0 TI 25 NLNHFJJO--O CH: O NH-C OSC4Hnn 5:: N pr. 0 0

NiNH-C O-O OHa /C\ O NIH-C OSCn (7).::::: N pr. 0 0

NlNH-C O-O CH3 l /O\ o NH-C 0-- 0G 1 Piricularia test. 2 Pelliculariatest.

leaves present at the time of inoculation with Piricu'laria EXAMPLE 7oryzae is determined as a percentage of the untreated but alsoinoculated control plants. In the case of the plants infected withPellicularia sasaki, the infection on the leaf solvent: 47 parts byWeight acetone sileaths after the same 15 also determined propor'Emulsifier: 0.3 part by weight alkylaryl polyglycol ether tron of theuntreated but infected control. 0% means no Water: 950 parts by weightinfection; whereas 10% means that the infection is exactly The amount ofthe particular active compound required as great as in the case of thecontrol plants.

The particular active compounds tested, their concenfor e deslred lcPncemfatlon P Such actlve trations and the results obtained can be seenfrom the Pound the Spray llquld mlxed Wlth thefitated anilount follo iTable of solvent, and the resulting concentrate is then diluted with thestated amount of water containing the stated Addltional test/curativefungicidal action emulsifier.

In order to determine .the curative fungicidal action, Young appleseedlinges in the 4-6 leaf stage are sprayed the hereinbefore describedtestis repeated, the particular 7 with the given spray liquid untildripping wet. The plants Fusicladium test (apple scab) (Protective)remain in a green-house for 24 hours at 20 C. and at a relativeatmospheric humidity of 70%. Such plants are then inoculated with anaqueous conidium suspension of the apple scab causative organism(Fusicladium dendriticum and incubated for 18 hours in a humiditychamber kept at 18-20 C. and at a relative atmospheric humidity of 100%.

The plants are then again placed in a green-house for 14 days.

15 days after inoculation, the infestation of the seedlings isdetermined as a percentage of the untreated but also inoculated controlplants.

means no infestation; whereas 100% means that the infestation is exactlyas great as in the case of the control plants.

The particular active compounds tested, their concentrations and theresults obtained can be seen from the following Table 7.

TABLE 7,-FUSICLADIUM TEST (PROTECTIVE) Infection as of the infection 18weight of talc and kieselguhr to provide a finely powdered mixture withthe desired final concentration of such active compound.

Wheat seed is contaminated with g. of the chlamydospores of Tilletiacaries per kg. of seed. To apply the given dressing, the seed is shakenwith such dressing in a closed glass flask. The seed, on moist loamunder a cover of a layer of muslin and 2 cm. of moderately moist compostsoil, is exposed to optimum germination conditions for the spores fordays at 10 C. in a refrigerator.

The germination of the spores on the wheat grains, each of which iscontaminated with about 100,000 spores, is subsequently determinedmicroscopically. The smaller the number of spores which have germinated,the more eifective is the given active compound.

a percentage of the untreated control with a concentration of activecompound of- Active compound 0.025 0.0062 0.00156 (A) CO 6 10 32 NS-CC1:

(known) N NHCO-OCH:

| 0 NH-O o-s- NJ-NHCOOCHs l 0 NH-CO-O-CsHu-n NiNHCOOCHa I 0 NHCOSC4H nEXAMPLE 8 The particular active compounds tested, their concentration inthe dressing, the amounts of dressing used and To produce a suitable drydressing, the particular active the percentage spore germination can beseen from the compound is extended with a mixture of equal parts byfollowing Table 8.

Seed dressing test/bunt of wheat (seed-boron mycosis) TABLE 8.-SEEDDRESSING TEST/BUNT OF WHEAT Concentration of active compound in AmountSpore the dressing, applied oi germinapercent by dressing in tion inActive compound weight g./kg. seed percent Non-dressed 10 3 1 0.000 (2)-N 10 1 0.000 30 1 0. 000 NlNHO OO CH3 l C\ o NH-C os JNH--C 0-0 CH3 N lO NH-C OOCaHi1n J-NHC 00 CH:

N I C EXAMPLE 9 Agar plate test Test for fungitoxic efiectiveness andbreadth of the activity spectrum Solvent-acetone parts by Weight:

given active compound, the agar is poured into Petri dishes understerile conditions. When the mixture of substrate and active compoundhas solidified, test fungi from pure cultures are inoculated onto it insmall discs of 5 mm. diameter. The Petri dishes remain at 20 C. for 3days for incubation.

After this time, the inhibiting action of the active compound on themycelium growth is determined in categories, taking into account theuntreated control. 0 means no mycelium growth, either on the treatedsubstrate or on the inoculum; the symbol means mycelium growth on theinoculum only, no spread to the treated substrate; and the symbol meansmyoelium growth from the inoculum onto the treated substrate, similar tothe spread to the untreated substrate of the control.

The particular active compounds tested, their concentrations, the testfungi and the inhibition effects achieved can be seen from the followingtable 9.

TABLE 9.AGAR PLATE TEST Concentration of active Sclero- Verti- ThiclasFusar- Fuswrcompound in tiflifl cillium mopsis tum mm. the substratescleroalbobasiculoxy- Active compound in p.p.m. ttorum atrum cola morumsporum Untreated (2) 10 0 0 0 0 --TZ 0 0 O 0 0 NJNHCOOCHa I 0 O NH-G0-S- (3) 10 0 0 0 0 0 -TT 100 0 0 0 0 0 NJ-NHC OOCH;

l g 0 9A NH C 0 a n-n TABLE 9.AGAR PLATE TEST Concentration of activeSolerm Verti- Thiela Fusar- Fusarcompound in tt'm'a cillium 'uiopsis tumtum the substrate sclerobobasioul oxy- Aotive compound in p.p.m. t'iorumatrum cola morum sporum (4) 10 0 0 0 0 IN 100 0 0 0 0 0 \NJNHCOOCHI C ONHCOS-C|Hon 0 0 0 0 0 iv 100 0 0 0 0 0 \NJINH-CO-OCHH I 0 NH-C 0- SCnHas-n 1o 0 0 0 0 o N 100 o 0 o 0 0 NJ-NHCOOCHz 0 NHCOO H 'EXAMPLE 10Control dishes to which the active compound preparation has not beenadded are also set up.

111 r t t st Mycehu g ow h e When the nutrient medium has cooled andsolidified, ut lfi medium used: the dishes are inoculated with thespecies of fungi stated Part by in the table below and incubated atabout 21 C. Agar-agar (powdered) 2 Evaluation is carried out after 4-10days, dependent Malt extract 30 upon the rate of growth of the fungi.When evaluation is 2 950 carried out the radial growth of the myceliumon the Proportion of Solvent to nutrient medium: 4 treated nutrientmedia is compared with the growth on the control nutrient media. In theevaluation of the fungus A t Parts by growth, the followingcharacteristic values are used:

ce one Agar nutrient medium 100 0 no fungus growth 1 very stronginhibition of growth 2 medium inhibition of growth 3 slight inhibitionof growth 4 growth equal to that of untreated control.

The particular active compounds tested, their concentrations, and theresults obtained can be seen from the following Table 10.

TABLE 10.MYCELIUM GROWTH TEST Concentra- Phtalo- VertitlonotactiveFiriphom Hypooh- Oercocill'ium Fusarcompound calorie cine nus sporaalbotum Activecompound in p.p.m. oryzae 'resceits sasakii musae atrumdirmthi N-S-C0la C ll 0 (known) T NLNHC O-0CHs o NH-CO-SQ TABLE10.-MYCELIUM GROWTH TEST Coneentra- Phialo- Vertition ofaetive PM; phomHypoch- Oercocillium Fusarcompound, culam'a cinenus spam albotum. Activecompound in p.p.m. org ewe rescens sasalm musae wtrum diantht' INJNHOO-OCH:

l C O NH-O OO-CaH11-' I NJNH-C OOOH:

I 0 NHCOSC4H0 F NJNHC O-OCH1 l C O NH--C OS 012 15 T NJ-NH-CO-OCHa l C 0NH-COS EXAMPLE '11 trations of the given active compound, with referenceto Podosphaera test (systemic) Solvent: 4.7 parts by Weight acetoneEmulsifier: 0.3 part by weight alkylaryl polyglycol ether Water: 95.0parts by weight 100 cc. of soil. The plants thus treated are, aftertreatment, inoculated with conidia of Podosphaera leucotricha SaIm. andplaced in a greenhouse kept at a temperature of 21-23 C. and at arelative atmospheric humidity of about Ten days after the inoculation,the infection of the seedlings is determined as a percentage of theuntreated but also inoculated control plants.

0% means no infestation; whereas means that the infection is exactly asgreat as in the case of the control plants.

The particular active compounds tested, their concentrations and theresults obtained can be seen from the following Table 11.

TABLE 11.PODOSPHAERA TEST (SYSTEMIC) Infection as a percentage of theinfection of the untreated control with a concentration of activeconpound (in percent) 26 TABLE 11--Podosphaera Test (Systemic) Infectionas a percentage of the infection of the untreated control with aconcentration of active eornpound (in percent) Active compound 120p.p.m. 30 p.p.m.

I NH-C-OCH I 0 C O NH-C-OOaHn-n l NHC-OC'H O 0 O NH'-fiS-C4Hn-l'l lNH-OOOH i H z I 0 O N H|J S CnHra-fl J (I? N NH-COCHa J'- (H) NNH-G-OCHa l o NH--(l'[JO-C(CH3);

The following further examples illustrate, without 1imi EXAMPLE 13tation, the process for producing the particular new compounds of thepresent invention.

0 The above compound is obtained in accordance with the 1 particularsgiven in Example 12. Melting point: 210 C.

19.1 g. 0.1 mole) benzimidazole-Z-carbamic acid (with methyl ester and21.9 g. (0.1 mole) 4-tert.-butylphenoxycarbonylisocyanate are stirredtogether in 750 ml. dry EXAMPLE 14 chloroform for 5 hours at roomtemperature. During this time the starting materials have dissolved,except for a small residue. Filtration is elfected and the filtrate isevaporated in a vacuum. The residue is washed with cyclo- LNHAXLO CH3hexane and dried. 1-[N-(p-tert.-butylphenoxycarbonyl)-carbamidyH-benzimidazole 2 yl-carbamic acid methyl l ester of themelting point 160C. (with decomposition) j N is obtained. Yield 40 g.,that is 97% of the theory. 0 u e (3) The above compound is obtained inaccordance with the particulars given in Example 12. Melting point: 175C. (with decomposition).

EXAMPLE 15 The above compound is obtained in accordance with theparticulars given in Example 12. Melting point: 195 C. (withdecomposition).

EXAMPLE 16 decomposition).

EXAMPLE 17 NH-C o-o-@ The above compound is obtained in accordance withthe particulars given in Example 12. Melting point 170 C. (withdecomposition).

Another compound of the invention is l-[N-(phenoxycarbonyl)-carbamidyl]benzimidazole-2-yl carbamic acid methyl ester.

It will be realized by the artisan that all of the foregoing compoundscontemplated by the present invention possess the desired strongfungicidal properties, with regard to a broad spectrum of activity, aswell as a comparatively low toxicity toward warm-blooded creatures and aconcomitantly low phytotoxicity, enabling such compounds to be used withcorrespondingly favorable compatibility with warm-blooded creatures andplants for more eifective control and/or elimination of fungi byapplication of such compounds to such fungi and/ or their habitat.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:

1. A benzimidazole derivative of the formula 11 @QLnn-g-o-a is which Xstands for oxygen or sulfur,

R stands for loweralkyl, and

R stands for alkyl of to 12 carbon atoms when X stands for oxygen, orfor alkyl or 1 to 12 carbon atoms when X stands for sulfur, or forcycloalkyl of 5 to 12 carbon atoms, or for phenyl or 4-tert.butylphenyl. 2. A compound according to claim 1 in which R stands 28 foralkyl of 1 to 3 carbon atoms and R stands for n-butyl, n-octyl,n-dodecyl or for phenyl or cyclohexyl.

3. Compound according to claim 1 wherein such compound is 1 [N(phenylmercaptocarbonyl)-1carbamidyl]-benzimidazole-2-yl-carbamic acidmethyl ester of the formula 4. Compound according to claim 1 whereinsuch compound isl-[N-(n-octoxycanbonyl)-carbamidyl[-benzimidazole-2-yl-carbamic acidmethyl ester of the formula 5. Compound according to claim 1 whereinsuch compound is 1 [N-(n-butylrnercaptocarbonyl)-carbamidyl]-benzimidazole-2-yl-carbamic acid methyl ester of the formula 6. Compoundaccording to claim 1 wherein such compound is 1 [N (ndodecylmercaptocarbonyl)-carbamidyl]-benzimidaZOIe-Z-yI-carbamic acidmethyl ester of the formula 7. Compound according to claim 1 whereinsuch compound is 1 [N (cyclohexyloxycarbonyl)-carbamidy1]-benzimidazole-Z-yl-carbamic acid methyl ester of the formulabenzimidazole-Z-yl-carbamic acid methyl ester of the formula References(Iited UNITED STATES PATENTS 4/ 1960 Klopping 260-3 09.2

11/1961 Loux 260-3092 11/1970 Klopping 260-3092 4/ 1971 Actor 260-30925/ 1972 Dittmar 260-3092 FOREIGN PATENTS 11/ 1970 France 260-3092NATALIE TROUSOF, Primary Examiner US. Cl. X.R.

292 33 UNm-LD S'LA'IES PATENT 0mm;

'CERTEHPICATE OF CGRREC'HON Patent m 3,711,503 w Dated January 16, 1973Invent0r(s) Arno Widdig et al (P g 1 of 5) It is certified .that errorappears in the above-identified patent and that: said Letters Patent arehereby corrected as shown below:

Col. 1., line 5 0, ineert (1) after the forrnula Col. 5, line 17,correct spelling of "formulation". Colo 7, Table 2', compound (2)formulajsho uld read i H 3 O U C91. 8, Table 2 change heading to read I--=Infection as a percentage of the infection of the Untreated controlwith a concentration of active I compound of l20 p.p.'m. Col.- 9, line4, cor-rectspelling of "se'en'H Col. 10, Table 3, under heading of"Infection as a percentage of the untreated control", insert O after"compound (2) Col. l3, Table 5, change compound number "(7) "to-- (l)Col. 15, 'line 64, correct spelling of "sasakii I Col. l5, line 66,change; "of" to to Col. 15, line 67, change "10%",co 100% insert --7--.

W050 UNITED STATES PATENT OFFICE CERTIFICATE OF CORREC HON Patent No.3,711,503 Dated Januaryv 16 19 73 Inventoflls) Arno 'widdig et a1 (page2 of 3) It is certified-that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

E01. l6, line 74, correcl't spelling of "seedlings".

C01,, 17, line 73, change "boron" to '--born-- Col, 21, Table9,lasfcompound, ima in 6),- Col. 23, Table 10 Componnd (7) should read Col.25, Table ll, Compound (6), underheading of "120 p.p.m."

Col 25 Table change compound "(7)" to -(l)----.

Col. 27, line 65, insert (I) after' formula.

.Col.' 28,"elaim-3, formula shonld read M Im CO-SQ UNITED STATES PATENTorwcn QERTEFKCATE OF QQRREQTION Patent 3 ,711 ,503 Dated January 16 1973Inventor(s) Arno Widding et 31 (age 5 0f 3) It is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below: I

Col. 28, claim 6, compound should read H N NH--C-OCH3 "1) NH 8 S 12 25Signed and sealed this 18th day of December 1975.

(SEAL) Attest:

PDWARD M FLFTPHFR I TR RPNF D TFGTMFYFR Attesting Officer 1 ActingCommissioner of Patents

